Method of preparing uranium hydride



W, 1948. A. s. NEWTON 2,446,780

METHOD OF PREPARING URANIUM HYDRIDE Filed July 22, 1944 frimento r mos .5. Wen/to 11/ flown/3y Patented Aug. 10, 1948 IWE'THOD F PREPARING URANIUM HYDRIDE Amos S. Newton, Ames, Eowa, assignor to the United States of America as represented by the United States Atomic Energy Commission Application July 22, 1944, Serial No. 546,178

3 Claims. 1

The invention relates to the preparation of uranium hydride.

It is an object of the invention to provide an improved and inexpensive process for producing uranium hydride in a rapid and eilicient manner. A further specific object is the provision of a process for preparing uranium hydride by reaction of uranium with hydrogen under conditions such that pressures developed during the process provide a means by which completion of the reaction between uranium and hydrogen may be visibly indicated. Further objects and advantages of the invention will appear from the following description and drawing appended thereto.

Prior to the present invention other processes have been suggested for the production of uranium hydride. For example, U. S. Letters Patent granted to Frank H. Driggs No. 1,816,830, granted August 4, 1931, describes a process in which powdered uranium metal is introduced into a hermetically sealed container, the container evacuated and the powder degasified, and subsequently this degasiiied powder is reacted with hydrogen to form uranium hydride. This process has been open to several objections. For example, the amount of air and other gases adsorbed by the powder is substantial and in consequence, a considerable period of degasification has been necessary in order to secure proper reaction. Furthermore, since hydrogen tends to react with powdered uranium spontaneously with evolution of much heat, the reaction often is very difficult to control, and may even become explosively violent.

Recognizing the objections to this process, Briggs proposed an improvement in U. S. Letters Patent No. 1,835,024, granted December 8, 1931. In this patent Driggs pointed out that the necessary degasiiication of metallic powder materially increases the .cost of manufacture and suggested a step by step process of formation of the hydride. In accordance with this process, uranium powder was sintered to form an essentially coherent solid body of uranium, and this body was subjected to the action of hydrogen in the usual manner. Uranium hydride formed as a coating upon the surface of the sintered uranium until the surface became completely coated whereupon reaction ceased. Thereafter the coated uranium was subjected to heat to cause decomposition of the hydride and formation of uranium metal in powdered state which fell to the bottom of the reaction chamber exposing fresh uranium surface of the coherent uranium mass. Hydrogen was again introduced into the reactor, and the powdered metal hydrogenated to form uranium hydride which was withdrawn from the reactor. The two step process is repeated as often as is required to convert the sintered uranium body to uranium hydride.

It is apparent that this process ofiers certain complications due to the fact that a two stage operation is necessary thus materially decreasing the rate of formation of uranium hydride and increasing the cost of the process. In accordance with the present invention, many of the diificulties in prior art methods have been eliminated and a process which may be conducted in an essentially continuous manner developed. I have found that by reaction of hydrogen with massive or dense metallic uranium which is substantially free from oxide parting planes in the interior of the uranium mass, the reaction may be conducted continuously and without recourse to an intermediate stage wherein the hydride is decomposed. Thus I have ascertained that, upon reaction of hydrogen with massive or dense metallic ura nium, the uranium hydride is formed in an essentially pulverulent state which crumbles and falls from the uranium surface thereby continuously exposing fresh uranium to the action of hydrogen. In such a case the reaction may be continued so long as metallic uranium is present.

The metallic uranium used in accordance with this invention may be of high purity, or may be physically mixed, contaminated, or alloyed with other materials such as tin, copper, bismuth, aluminum, silver, or gold. For example uranium alloys with these metals or uranium containing these metals in dendrite form preferably wherein the uranium is in the preponderant concentration may be treated in accordance with this invention. Moreover the uranium may contain other materials so long as it is essentially free from internal oxide parting planes. Such uranium or at least the uranium content of uranium mixtures has a purity such that it has a melting point not in excess of about 1200 degrees C., is free from oxide parting planes and in consequence has a density of above 18 grams per cubic centimeter.

Oxide free uranium in massive state suitable for use in accordance with this invention may be prepared by reduction of uranium salts under conditions such that the metallic uranium formed becomes molten and drains or stratifies to form a pool, from which the impurities separate and collect as a slag layer. Upon solidification of the pool the metal secured is dense and essentially massive metal. For example, uranium tetrafiuoride or similar halide may be reacted with an alkaline 3 earth metal, such as magnesium or calcium, with consequent formation of the alkaline earth fluo ride and metallic uranium at a temperature sufficiently high to melt the uranium and cause it to separate from the fluoride into a molten metallic uranium pool.

The hydriding reaction with such massive metal is preferably conducted in a closed system in order that oxygen, air and other impurities may be excluded at least to a substantial degree. It may be especially effectively conducted in a more or less automatic manner by introducting the hydrogen at a controlled rate approximately equal to the rate of consumption of hydrogen in the reaction and observing the pressure established within the system. By this means it is possible to ascertain the time at which the reaction becomes complete since at such time thehydrogen introduced will tend to increase the pressure within the system, and the time of pressure increase will denote the time of reaction completion.

The invention will be more clearly understood by reference to the accompanying drawing which is a diagrammatic sectional view of a suitable apparatus for carrying out the process.

As shown in the drawing, one example of a suitable apparatus for providing closed system I includes a source of water or water vapor such as container 2 which contains water 3 in an amount sufficient to yield, by reduction of the water vapor, the quantity of hydrogen necessary for the formation of uranium hydride by subsequent reaction of the hydrogen and uranium. To increase the vaporization of water 3 over that obtained at room temperature, water bath 4 heated by suitable heating means (not shown), is provided, the water bath 4 raising the temperature of water 3 above room temperature, as for example to approximately 30 degrees C. Water vapor from container 2 is admitted to the system through stopcock 6.

For passage of the water vapor, tube 1 extends from container 2 into chamber 8, the chamber 8 containing a reducing agent 9. The reducing agent may be iron, zinc or other material conventionally used for obtaining of hydrogen .by the reduction of water, the reducing agent reacting with the water vapor to form gaseous hydrogen and an oxide of the reducing agent. Metallic uranium has been found to be particularly suitable for this purpose as it is highly reactive with water vapor and causes a substantially complete reduction thereof. The reducing agent is preferably in a form, such as metallic Wool or turnings, that presents a large surface area to the Water vapor coming from tube 1, and is so arranged in reduction chamber 8 as to readily contact the water vapor passing through the chamber. Where metallic uranium is used as a reducing agent, stable formation of uranium hydride in chamber 8 is prevented by the high temperature therein.

The chamber 8 is surrounded by heating means H which may be, for example, of conventional electric furnace construction and in the simplest form may comprise furnace casing [2 containing electricheating elements l3. Heating means I! is adapted to maintain chamber 8 at a suitable temperature for example 600 to 800 degrees C, to cause a reduction of the water vapor by reducing agent 9, and includes suitable and customary control means, not shown,

.for maintaining the chamber'at the desired temperatures.

The hydrogen resulting from the reduction of the water vapor by reducing agent 9 is conveyed from chamber 8 through tube M, which extends into trap 56. The trap it removes unreduced water vapor carried by the hydrogen, the purification being effected by maintaining the trap at low temperatures, thereby causing condensation of any water vapor present. The trap is cooled by suitable cooling liquid in receptacle 15 such as, for example, solid carbon dioxide I7. and acetone l8, liquid air,v liquid oxygen, or the like.

The dried hydrogen is conveyed from trap 16 into chamber 22 through tube l9, which includes stopcock 2i which may be used to close off chamber 22 from the remainder of the system.

Chamber 22 contains metallic uranium 23, in massive or dense state and free from internal oxide parting planes preferably, in the form of turnings, for example, with which the hydrogen generated in chamber 8 reacts to produce uranium hydride. The chamber 22 is surrounded by heating means 24 comprising casing 25 containing heating elements 21. Heating means 2 4 is adapted to maintain chamber 22 at a suitable temperature, such as, for example, a temperature between degrees C. and 400 degrees C., to cause a reasonably rapid rate of reaction between the hydrogen, generated in chamber 8, and the metallic uranium in chamber 22. Heating means 24, like heating means H, includes suitable and conventional means, not shown, for controlling the temperature of the furnace.

As it is desirable to remove atmospheric oxygen from the system before carrying out the process, chamber 22 may include outlet tube 23 which is connected to any conventional type of mechanical exhaust means, not shown, capable of obtaining a vacuum in the system of the order .1 mm, mercury pressure. After evacuation, stopcook 29 is closed thereby closing the entire system. In lieu of evacuation, the system may be flushed out with hydrogen while chamber 22 is unheated by passing water vapor into heated chamber 8 with stopcocks 2i and 29 open. The resulting hydrogen is forced through trap l6 and chamber 22, passing out through exhaust tube 23, After the system has been completely flushed with hydrogen, stopcock 25 is closed and chamber 22 is heated to the most favorable temperature for the formation of uranium hydride.

Manometer 3! or equivalent pressure indicating means may be connected to the system on an extension of tube 1 to visually indicate the pressures developed during the process. The various elements of the apparatus are suitably formed of a material, such as heat resistant glass, glass lined iron, stainless steel, etc., that withstands elevated temperatures, resists corrosion, and does not contaminate or react with the substances present in the system,

In the performance of the process embodying the invention, stopcock 6 is closed, stopcocks 2| and 29 are opened, and the system is evacuated through tube 28. After a sufficient vacuum has been obtained, stopcock 29 is closed, thereby closing the system. Water 3 is heated by bath 4 to above room temperature, such as, for example, to approximately 30 degrees C., and stopcock G is opened to admit the water vapor from container 2 to chamber 8 through tube I. Chamber 8, containing the reducing agent 9, is maintained by heating means H at a suitable temperature, such as, for example, between 600 degrees C., and

800 degrees 0., for the reduction of the water vapor. The hydrogen resulting from the reduction of the water vapor in chamber 8 passes through tube M into trap IS in which any water vapor carried by the hydrogen is condensed.

The dried hydrogen is conveyed by tube Hi from the trap 16 into chamber 22, maintained at a suitable temperature by furnace 24, in which i it reacts with metallic uranium 23 to form uranium hydride. In general, the reaction proceeds more rapidly as the temperature of and pressure in chamber 22 is increased, the pressure in chamber 22 being automatically controlled by the generation of the hydrogen in the closed system. The reaction proceeds satisfactorily where chamber 22 is maintained at a temperature of between 200 degrees C, and 400 degrees C. As the reaction takes place, the uranium hydride tends to fall away from the uranium metal thereby exposing additional uranium metal for further reaction. The reaction continues until all of the uranium is converted to uranium hydride. As an example of the rate of conversion of metallic uranium to uranium hydride where the chamber 22 is maintained at a temperature between 250 degrees C. and 300 degrees 0., 100 grams of uranium turnings were converted to uranium hydride in less than thirty minutes and a 100 gram lump of uranium metal was converted to uranium hydride in less than two hours.

After conversion of the uranium metal to uranium hydride is substantially complete, the pressure in the system increases rapidly as the supply of hydrogen to the system continues, such increased pressure in the system being visibly indicated by manometer 3!. Stopcock 2! is then closed to seal off chamber 22 from the remainder of the system I and to permit removal of the uranium hydride. Stopcock 6 is also closed to prevent further generation of hydrogen in chamber 8. The uranium hydride is preferably cooled in the atmosphere of hydrogenpresent in the chamber 22 in order to prevent or minimize decomposition thereof. Where stopcock 2| is not provided, chamber 8 should be maintained at a lower temperature than that of chamber 22 during the cooling of the uranium hydride or other means utilized to prevent distillation of hydrogen from chamber 22 into reduction chamber 8 and consequent decomposition of the uranium hydride during cooling.

The pressure established in the chamber 22 during hydrogenation and cooling is controlled at approximately the decomposition pressure of the uranium hydride or somewhat above this pressure. Thus at a temperature of approximately 300 degrees C., the decomposition pressure of the uranium hydride is approximately 24 mm. and the uranium hydride formed will decompose into hydrogen and uranium metal at this temperature whenever the hydrogen pressure is below this value. During the operation of the process, continud introduction of hydrogen into the reaction chamber causes the pressure to increase until it exceeds the decomposition pressure and uranium hydride formation is initiated. As the hydrogen combines with the uranium, the pressure in chamber 22 tends to decrease and if the hydrogen pressure goes below the decomposition pres sure, the formation of uranium hydride diminishes or ceases until further hydrogen is supplied to the system and the pressure is increased to above the decomposition pressure whereupon hy dride formation proceeds.

This afiords a simple and eifective means for controlling the rate of hydride formation and for determining the time at which the reaction is completed. Thus at the start of the reaction hydrogen is supplied to chamber 22 in amount sufiicient to establish hydrogen pressure in excess of the decomposition pressure but insufiicient to cause the hydrogenation reaction to occur more or less explosively. Usually a pressure which is not over about 150 millimeters above the decomposition pressure is established. In general hydrogen is introduced substantially as rapidly as it is consumed and at a rate suficient to replace consumed hydrogen and to maintain the hydrogen pressure within the system above the decomposition pressure at the reaction temperature generally at a constant value within the desired pressure range.

The following table lists the approximate decomposition pressure of uranium hydride at various pressures and at various temperatures and illustrates the minimum hydrogen pressure which may be used at any particular temperature.

Decomposition Pres- 808 mm. of Hg:

After the reaction has been completed, the hydrogen introduced causes the pressure to increase thus afiording a simple method of determining the time at which the hydride formation is completed since the pressure increase will be visually indicated by the manometer.

The generation of hydrogen Within the system as herein described is especially advantageous since it avoids establishment of high concentrations of hydrogen and permits a more or less automatic means of control. Use of metallic uranium to generate hydrogen is especially effective since it reacts with Water vapor, to form hydrogen and an oxide of uranium with unusual reactivity and the reaction requires little control. Where uranium metal in the form of turnings, or other form presenting substantial surface for contact, is used as the reducing agent, substantially complete reduction of the water vapor by the uranium generally occurs and gaseous hydrogen containing little or no water vapor is obtained thus minimizing the importance of the trap l5, and minimizing difficulties encountered by presence of moisture. Preferably, the uranium metal is used in an amount or an excess of an amount suificient to reduce all of the Water vapor admitted to the system.

The following example is illustrative.

Example 2015 grams of powdered uranium tetrafiuoride, having a particle size such that 90 per cent passes a 60 mesh screen, 85 per cent passes an mesh screen and 50 per cent passes a 200 mesh screen, was mixed with 400 grams of metallic magnesium having a particle size of about 20 mesh, the charge packed in an iron crucible lined with calcium oxide and the crucible closed. The crucible was gradually heated until it reached an outside temperature of about 640 degrees C. Molten metallic uranium and magnesium fluoride. formed". andnthe temperature: within-:the re-"*- actor was maintained "sufiicientlythigh 'toi main-' the uraniumxina molten state until the:

tain uranium separated amolterr pool in the bote tomofthe' crucible withthe magnesium fluoride on the top ofthe pool 'asa separate layer. Upon solidification the uraniumwas: secured inzmas sive state.

1910.2 gram per cubiccentimeter;

About 100 grams of thisuranium was' formed into turnings and was placed in chamber 22. 300 grams of uranium metal'ilyalso in the form of turnings, were placed in. chamberuii. Contamer 2 was partially filled withrwater and the container 2 heated to approximately 39 degrees C. by bath 4. Receptacle H) was filled withdry ice and acetone. With stopcoclz'ii closed and stopcocss 2i and 29 open, a vacuurn 'of the order of 0.1 min. was obtained in the system by"evacuating means attached to outlet tube' 28.- Stopcock 29 was then closed; chamber 8 heated"toapproximately 700 degrees..C.. .by. heating. means ii and chamber 22 heated to approximately 250 degrees C. by the heating means 24! Thereupon stopcock 6 was opened,water vapordeliveredto chamber 8 and theprocessconducted as pre' viously described. The conversion ofth'e metallic uranium 23 -touranium hydride was substantiallycomplete in two and a half hours; the completion of the reaction being indicated by rise in pressure in manometer 3i;

bled, and the uranium hydride in'the amount of 101.27 grams was removed.

The uranium hydride obtained-fromthe process of my invention is a finely dividedblack or brownish-black powder, having an absolute density of approximately 11 grams .per cubic centimeter. The bulk density of dryypowdered uranium hydride is approximately 3.4 grams per cubic centimeter. Where the uranium'hydride powder is pressedin an atmosphere of car-* bon dioxide under a pressure-of 28 tons'per squareinch, a block is obtained having adensity of ap-;

proXimat-ely 7.3 grams per cubic centimeter: Such uranium hydride block has an appearance of pressed metal although it is fragile and easily chipped.

Uranium hydride decomposes to form metallic uranium powder and hydrogen, if heated; The ecomposition pressure of uranium: hydride varies from approximately 4 'mm. to 809mm. ver a temperature range of from 252 degreesC. to 438 degrees C. The decomposition pressure is approximately one atmosphereat 436 degrees C.

The term uranium as usedin the following claims is intended to include metallic uranium; physical mixtures of uranium with other-material, such as tin or other'metallic dendrites, and. alloy forms in which uranium is the predominant constituent.

Although the present invention has been described with particular reference to certain of the specific details of certain embodiments thereof it is not intended that'suchi details shall 'be regarded as limitations upon the scope ofr'the lhis uranium :metal had a melting point of 11001-25 degreesr'C.,:and aidensity. or.-

Stopcock- 2 l was closed, the apparatus cooled'and-disassem- I invention except in so far'as included in the ac companying claims.

Iclaim: 1. A method of preparing uranium hydride whichcomprises vaporizing water and supplying the vaporto a reaction zone in a closed system maintained below atmospheric pressure, reducingthe Water vapor to form hydrogen in said reaction zone, conducting the hydrogen to a second reaction zone in said system and reacting the hydrogen with metallic uranium and controlling the pressure within the system by controlling the temperature of the water undergoing vaporization.

2. A method of preparing uranium hydride tion zone and maintaining the uranium in the vvsecond zone at a temperature such that uranium hydride is formed.

3. A method of preparing uranium hydride which comprises establishing a pair of intercommunicating reaction zones, introducing an agent capable of reducing water vapor in the first of said zones, and uranium metal into the second'of said zones, introducing water vapor into the first zone and establishing a temperature thereinsufiicient to generate hydrogen from the Water-vapor, continuing introduction of further water vapor'into the first zone forcing evolved hydrogen into the second reaction zone, maintainingthe uranium in the second zone at a tern perature such that uranium hydride is formed and suppl ying the water vapor to the first reaction zone at a rate sufficiently slow to permit the pressure within the second reaction zone to ren'iain' below atmospheric pressure during the reaction.

AMOS S. NEWTON.

REFERENCES CITED The foliowing references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 222,843 Schuessler Dec. 23, 1879 963,484 Tait July 5, 1910 1,565,249 Berry Dec. 15, 1925 1,816,830 Driggs Aug. 4, 1931 1,835,024- Driggs Dec. 3, 1931 OTHER REFERENCES Babor'and Lehrman, General College Chemistry, 2nd ed., Thomas J. Crowell 00., N. Y. (1941)), pp. 149-50. 

